EP1546060A2 - Suspensions - Google Patents

Suspensions

Info

Publication number
EP1546060A2
EP1546060A2 EP03792403A EP03792403A EP1546060A2 EP 1546060 A2 EP1546060 A2 EP 1546060A2 EP 03792403 A EP03792403 A EP 03792403A EP 03792403 A EP03792403 A EP 03792403A EP 1546060 A2 EP1546060 A2 EP 1546060A2
Authority
EP
European Patent Office
Prior art keywords
suspensions
aluminum sulfate
weight
bentonite
setting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP03792403A
Other languages
German (de)
French (fr)
Inventor
Rudolf Lunkenheimer
Hubert DÖRRER
Jochen Stein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kurita Water Industries Ltd
Original Assignee
BK Giulini GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BK Giulini GmbH filed Critical BK Giulini GmbH
Publication of EP1546060A2 publication Critical patent/EP1546060A2/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/148—Aluminium-sulfate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
    • C04B2111/00172—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite by the wet process
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1006—Absence of well-defined organic compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1025—Alkali-free or very low alkali-content materials

Definitions

  • the present invention relates to suspensions, their preparation and their use to accelerate the setting and hardening of cement and mixtures containing it.
  • Shotcrete has to set very quickly, e.g. to guarantee the highest level of security and smooth tunneling during tunnel construction.
  • Setting accelerators are used for this purpose.
  • Alkaline accelerators are highly caustic and therefore hazardous to health, they reduce the final strength of the concrete and force the shrinkage, which can lead to increased crack formation.
  • the alkali metals of these accelerators can be washed out, which can lead to contamination of ground and drinking water and to the increased sintering of drainage.
  • Aluminum sulfate and aluminum hydroxysulfates are based.
  • Aluminum sulfate is well suited as a setting accelerator, although it is technically of great advantage to provide the setting accelerator in liquid form. Due to the low water solubility of aluminum sulfate of approximately 8% by weight as Al O 3 , large amounts of the aluminum sulfate solution would be necessary to achieve the above-mentioned
  • the accelerators described above are offered both as powders and as liquids (solution or suspension), whereby in any case the liquid products are preferable to the powders because of their better meterability, the more homogeneous distribution and faster release of the active substance.
  • EP 0 812 812 AI and US 5,935,318 describe an accelerating additive for cementitious compositions which contains aluminum sulfate, largely free of aluminum hydroxide, and at least one alkanolamine.
  • the accelerating additive can also contain a stabilizer selected from polymer dispersions or sepiolite.
  • EP 0 858 981 A1 describes a setting and hardening accelerator containing aluminum salt, preferably Al 2 (SO 4 ) 3; claimed, which is characterized in that it contains a) amorphous silica and b) an inorganic and / or organic thixotropic agent and / or an organic carbonic acid ester.
  • This accelerator necessarily requires at least three components, using both organic and inorganic thickeners to keep the amorphous silica in suspension.
  • Organic thickeners are described here by way of example, but bentonite is also mentioned as the inorganic thickener.
  • the concentrations of the aluminum salts are also significantly below 8% by weight, so that relatively large amounts of the accelerating solution are necessary, which has a negative effect on the water / cement Ratio affects.
  • the present invention was therefore based on the object of providing the market with a setting and hardening accelerator in liquid form which is free or almost free of COD-containing substances and has good effectiveness.
  • suspensions which are characterized in that they contain aluminum sulfate in amounts of more than 8% by weight as Al 2 O 3 and suspended or dispersed bentonite in amounts of 1 to 7% by weight , In contrast to the prior art products cited above, these suspensions contain neither alkanolamines nor amorphous silica, nor organic thixotropic agents.
  • suspensions is understood to mean systems which consist of several phases, one of which is continuous and at least one further is finely divided, the finely divided phase predominantly comprising solid particles with a particle size of less than 100 ⁇ m, preferably less than 70 ⁇ m.
  • the suspensions are produced by a process which is characterized in that aluminum sulfate, which is partly in solid form, is stirred in the presence of bentonite in water at elevated temperatures, preferably at temperatures up to 100 ° C., so that a suspension is formed ,
  • aluminum sulfate includes compounds of the formula
  • the aluminum sulfate is used in an amount of more than 8% by weight to 15% by weight, in particular 10 to 12% by weight, based on Al O 3 .
  • Ca, Ca / Na and Na bentonites are preferred as bentonites, which in
  • Water are dispersible. In particular, an amount of 2 to 6% by weight is used.
  • the suspensions are prepared by introducing water into a reactor equipped with a stirrer, stirring aluminum sulfate in solid form and bentonite and homogeneously suspending both components at room temperature, preferably at elevated temperature. A large proportion of the aluminum sulfate dissolves, the rest is later in suspension, the suspended portions being stabilized by bentonite with regard to sedimentation.
  • a preferred method is characterized in that bentonite is suspended in an aluminum sulfate solution in a first step, and solid aluminum sulfate is added to this suspension in a second step, and this is then homogeneously suspended at elevated temperature.
  • the temperature does not exceed 100 ° C.
  • the suspension is prepared so that a
  • Aluminum sulfate is stirred in as a solid material with high shear rate.
  • the suspension is then heated to 70 ° C, a further 15 to 120 min. with the
  • Toothed washer stirred and cooled.
  • the end product has an aluminum sulfate content, expressed as Al O 3 , of over
  • the suspensions are preferably used in the range from 1 to 15%, based on the binder.
  • a commercially available suspension (Meyco SA 160, MBT - Switzerland) with an Al 2 O 3 content of 10.3% by weight and a COD content of 99 g / kg served as a comparison.
  • the suspensions according to the invention have advantages over the comparison in the Vicat test.
  • the content of amorphous silica must be at least 5% by weight.
  • the setting accelerator can contain up to 5% by weight bentonite.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to suspensions, to the production of said suspensions, and to the use thereof for accelerating the setting and hardening of cement and mixtures containing the same. According to the invention, said suspensions consist of aluminium sulphate in a quantity of more than 8 wt. % as Al2O3, preferably between 10 and 12 wt. %, and of suspended bentonite in a quantity of between 1 and 7 wt. %. Said suspensions can especially be used as economical and ecological alternatives in the field of wet spraying. The inventive suspensions are free of COD and alkali.

Description

SUSPENSIONEN SUSPENSIONS
Gegenstand der vorliegenden Erfindung sind Suspensionen, deren Herstellung und Verwendung zur Beschleunigung des Abbindens und Erhärtens von Zement und diesen enthaltenden Gemische.The present invention relates to suspensions, their preparation and their use to accelerate the setting and hardening of cement and mixtures containing it.
Mittel zum Beschleunigen des Abbindens und Erhärtens von Zement sind seit langem bekannt und werden in verschiedenen Bereichen eingesetzt, wobei im besonderen der Spritzbeton erwähnenswert ist.Means for accelerating the setting and hardening of cement have been known for a long time and are used in various areas, the sprayed concrete being particularly worth mentioning.
Spritzbeton muss sehr schnell abbinden, um z.B. beim Tunnelbau höchste Sicherung und einen reibungslosen Vortrieb zu gewährleisten. Zu diesem Zweck werden Abbindebeschleuniger eingesetzt.Shotcrete has to set very quickly, e.g. to guarantee the highest level of security and smooth tunneling during tunnel construction. Setting accelerators are used for this purpose.
Aus arbeitshygienischer und betontechnologischer Sicht wird der Einsatz klassischer alkalischer Abbindebeschleuniger wie z.B. Natriumaluminat und Wasserglas, immer stärker reduziert. Alkalische Beschleuniger sind stark ätzend und damit gesundheitsgefahrdend, sie reduzieren die Endfestigkeit des Betons und forcieren das Schwinden, was zu erhöhter Rissbildung führen kann. Die Alkalimetalle dieser Beschleuniger sind auswaschbar, was zur Verunreinigung von Grund- und Trinkwasser und zur verstärkten Versinterung von Drainagen fuhren kann.From a work hygiene and concrete technology perspective, the use of classic alkaline setting accelerators such as Sodium aluminate and water glass, increasingly reduced. Alkaline accelerators are highly caustic and therefore hazardous to health, they reduce the final strength of the concrete and force the shrinkage, which can lead to increased crack formation. The alkali metals of these accelerators can be washed out, which can lead to contamination of ground and drinking water and to the increased sintering of drainage.
Der Markt bietet entsprechende Alternativen an, die im wesentlichen aufThe market offers corresponding alternatives that are essentially based on
Aluminiumsulfat und Aluminiumhydroxysulfaten (basische Aluminiumsulfate) basieren.Aluminum sulfate and aluminum hydroxysulfates (basic aluminum sulfates) are based.
Aluminiumsulfat ist als Abbindebeschleuniger gut geeignet, wobei technisch von großem Vorteil ist, den Abbindebeschleuniger in flüssiger Form bereitzustellen. Bedingt durch die geringe Wasserlöslichkeit von Aluminiumsulfat von ca. 8 Gew.-% als Al O3 wären große Mengen an der Aluminiumsulfatlösung notwendig, um die oben erwähntenAluminum sulfate is well suited as a setting accelerator, although it is technically of great advantage to provide the setting accelerator in liquid form. Due to the low water solubility of aluminum sulfate of approximately 8% by weight as Al O 3 , large amounts of the aluminum sulfate solution would be necessary to achieve the above-mentioned
Anforderungen eines Abbinde-und Erhärtungsbeschleunigers zu gewährleisten.To ensure the requirements of a setting and hardening accelerator.
Dies hat zur Folge, dass speziell beim Nassspritzverfahren über dieThis has the consequence that especially in the wet spraying process via the
Aluminiumsulfatlösung große Wassermengen in den Beton eingebracht werden, die zu einer Erniedrigung der Druckfestigkeit führen. Höher konzentrierte flüssige Abbindebeschleuniger haben den Nachteil, dass sie organische Komponenten enthalten, die aufgrund ihrer Auswaschbarkeit aus dem Beton die Umwelt mit CSB-haltigen Stoffen belasten. Hierbei werden Carbonsäuren und Alkanolamine, vor allem Diethanolamin, welches schädlich für Wasserorganismen ist, eingesetzt.Aluminum sulfate solution, large amounts of water are introduced into the concrete, which lead to a reduction in the compressive strength. Highly concentrated liquid setting accelerators have the disadvantage that they contain organic components which, because they can be washed out of the concrete, pollute the environment with COD-containing substances. Here, carboxylic acids and alkanolamines, especially diethanolamine, which is harmful to aquatic organisms, are used.
Ein weiterer Nachteil dieser Produkte ist ihr hoher Preis, bedingt durch aufwendige Produktion bzw. hohe Rohstoffkosten. Die oben beschriebenen Beschleuniger werden sowohl als Pulver als auch als Flüssigkeiten (Lösung oder Suspension) angeboten, wobei in jedem Fall die Flüssigprodukte wegen ihrer besseren Dosierbarkeit, der homogeneren Verteilung und schnelleren Freigabe der Wirksubstanz den Pulvern vorzuziehen sind.Another disadvantage of these products is their high price, due to complex production and high raw material costs. The accelerators described above are offered both as powders and as liquids (solution or suspension), whereby in any case the liquid products are preferable to the powders because of their better meterability, the more homogeneous distribution and faster release of the active substance.
EP 0 812 812 AI und US 5,935,318 beschreiben ein beschleunigendes Zusatzmittel für zementartige Zusammensetzungen, das Aluminiumsulfat, weitgehend frei von Aluminiumhydroxyd, und mindestens ein Alkanolamin enthält. Das beschleunigende Zusatzmittel kann auch einen Stabilisator, ausgewählt aus Polymerdispersionen oder Sepiolith, enthalten.EP 0 812 812 AI and US 5,935,318 describe an accelerating additive for cementitious compositions which contains aluminum sulfate, largely free of aluminum hydroxide, and at least one alkanolamine. The accelerating additive can also contain a stabilizer selected from polymer dispersions or sepiolite.
In EP 0 858 981 AI wird ein Abbinde- und Erhärtungsbeschleuniger, enthaltend Aluminiumsalz, vorzugsweise Al2(SO4)3; beansprucht, der dadurch gekennzeichnet ist, dass er a) amorphe Kieselsäure und b) ein anorganisches und/oder organisches Thixotropiermittel und/oder einen organischen Kohlensäureester enthält. Dieser Beschleuniger benötigt notwendigerweise mindestens drei Komponenten, wobei sowohl organische als auch anorganische Verdickungsmittel verwendet werden, um die amorphe Kieselsäure in Suspension zu halten. Beispielhaft sind hier organische Verdickungsmittel beschrieben, wobei aber als anorganisches Verdickungsmittel auch Bentonit genannt wird. Wie in den Beispielen dieses Patentes offenbart wird, liegen zudem die Konzentrationen der Aluminiumsalze, ausgedrückt als Al2O3, deutlich unter 8 Gew. %, so dass relativ große Mengen an der beschleunigenden Lösung notwendig sind, was sich negativ auf das Wasser/Zement Verhältnis auswirkt.EP 0 858 981 A1 describes a setting and hardening accelerator containing aluminum salt, preferably Al 2 (SO 4 ) 3; claimed, which is characterized in that it contains a) amorphous silica and b) an inorganic and / or organic thixotropic agent and / or an organic carbonic acid ester. This accelerator necessarily requires at least three components, using both organic and inorganic thickeners to keep the amorphous silica in suspension. Organic thickeners are described here by way of example, but bentonite is also mentioned as the inorganic thickener. As disclosed in the examples of this patent, the concentrations of the aluminum salts, expressed as Al 2 O 3 , are also significantly below 8% by weight, so that relatively large amounts of the accelerating solution are necessary, which has a negative effect on the water / cement Ratio affects.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, dem Markt einen Abbinde- und Erhärtxingsbeschleuniger in flüssiger Form zur Verfügung zu stellen, der frei oder nahezu frei von CSB-haltigen Stoffen ist und über eine gute Wirksamkeit verfugt.The present invention was therefore based on the object of providing the market with a setting and hardening accelerator in liquid form which is free or almost free of COD-containing substances and has good effectiveness.
Die Aufgabe konnte überraschend durch die Bereitstellung von Suspensionen gelöst werden, die dadurch gekennzeichnet sind, dass sie Aluminiumsulfat in Mengen von über 8 Gew.-% als Al2O3 und suspendierten oder dispergierten Bentonit in Mengen von 1 bis 7 Gew.-% enthalten. Im Gegensatz zu den oben zitierten Produkten nach dem Stand der Technik enthalten diese Suspensionen weder Alkanolamine noch amorphe Kieselsäure, noch organische Thixotropiermittel.The task was surprisingly achieved by providing suspensions which are characterized in that they contain aluminum sulfate in amounts of more than 8% by weight as Al 2 O 3 and suspended or dispersed bentonite in amounts of 1 to 7% by weight , In contrast to the prior art products cited above, these suspensions contain neither alkanolamines nor amorphous silica, nor organic thixotropic agents.
Unter dem Begriff Suspensionen sind Systeme zu verstehen, die aus mehreren Phasen bestehen, von denen eine kontinuierlich und mindestens eine weitere feinverteilt ist, wobei die feinverteilte Phase überwiegend Feststoffteilchen mit einer Teilchengröße von unter 100 μm, vorzugsweise unter 70 μm, enthält.The term suspensions is understood to mean systems which consist of several phases, one of which is continuous and at least one further is finely divided, the finely divided phase predominantly comprising solid particles with a particle size of less than 100 μm, preferably less than 70 μm.
Die Suspensionen werden durch ein Verfahren hergestellt, das dadurch gekennzeichnet ist, dass Aluminiumsulfat, das zum Teil in fester Form vorliegt, in Gegenwart von Bentonit in Wasser bei erhöhten Temperaturen, bevorzugt bei Temperaturen bis 100°C, verrührt wird, so dass eine Suspension entsteht.The suspensions are produced by a process which is characterized in that aluminum sulfate, which is partly in solid form, is stirred in the presence of bentonite in water at elevated temperatures, preferably at temperatures up to 100 ° C., so that a suspension is formed ,
Unter dem Begriff Aluminiumsulfat sind Verbindungen der FormelThe term aluminum sulfate includes compounds of the formula
Al2 (OH)χ(SO4)v*zH2O, mit z = 0 bis 18, bevorzugt 10 bis 16, und y > 1,5 und x = 6 - 2y, zu verstehen.Al 2 (OH) χ (SO 4 ) v * zH 2 O, with z = 0 to 18, preferably 10 to 16, and y> 1.5 and x = 6-2y.
Das Aluminiumsulfat wird in einer Menge von über 8 Gew.-% bis 15 Gew.-%, insbesondere 10 bis 12 Gew. -%, bezogen auf Al O3, verwendet.The aluminum sulfate is used in an amount of more than 8% by weight to 15% by weight, in particular 10 to 12% by weight, based on Al O 3 .
Als Bentonite werden bevorzugt Ca-, Ca/Na- und Na-Bentonite verwendet, welche inCa, Ca / Na and Na bentonites are preferred as bentonites, which in
Wasser dispergierbar sind. Insbesondere wird eine Menge von 2 bis 6 Gew.-% eingesetzt.Water are dispersible. In particular, an amount of 2 to 6% by weight is used.
Die Suspensionen werden hergestellt, indem in einem Reaktor, ausgestattet mit Rührer, Wasser vorgelegt wird, Aluminiumsulfat in fester Form und Bentonit eingerührt werden und bei Raumtemperatur, bevorzugt bei erhöhter Temperatur beide Komponenten homogen suspendiert werden. Hierbei löst sich ein großer Anteil des Aluminiumsulfats, der Rest liegt später suspendiert vor, wobei die suspendierten Anteile durch Bentonit bezüglich Sedimentation stabilisiert werden.The suspensions are prepared by introducing water into a reactor equipped with a stirrer, stirring aluminum sulfate in solid form and bentonite and homogeneously suspending both components at room temperature, preferably at elevated temperature. A large proportion of the aluminum sulfate dissolves, the rest is later in suspension, the suspended portions being stabilized by bentonite with regard to sedimentation.
Ein bevorzugtes Verfahren ist dadurch gekennzeichnet, dass in einem ersten Schritt Bentonit in einer Aluminiumsulfatlösung suspendiert wird, und in einem zweiten Schritt festes Aluminiumsulfat zu dieser Suspension zugegeben wird, und dieses dann bei erhöhter Temperatur homogen suspendiert wird. Die Temperatur übersteigt dabei nicht 100 °C.A preferred method is characterized in that bentonite is suspended in an aluminum sulfate solution in a first step, and solid aluminum sulfate is added to this suspension in a second step, and this is then homogeneously suspended at elevated temperature. The temperature does not exceed 100 ° C.
In einer bevorzugten Form wird die Suspension so hergestellt, dass eineIn a preferred form, the suspension is prepared so that a
Aluminiumsulfatlösung mit einem Gehalt an Al O3 von etwa 8 Gew.-% beiAluminum sulfate solution with an Al O 3 content of about 8% by weight
Raumtemperatur vorgelegt und Bentonit mit einer Zahnscheibe eingerührt wird. Die entstehende Mischung wird auf 30 bis 35°C erwärmt, und das restlicheSubmitted to room temperature and bentonite is stirred in with a toothed lock washer. The resulting mixture is heated to 30 to 35 ° C, and the rest
Aluminiumsulfat wird als festes Material bei hohem Schergefälle eingerührt. DieAluminum sulfate is stirred in as a solid material with high shear rate. The
Suspension wird danach bis 70°C erwärmt, weitere 15 bis 120 min. mit derThe suspension is then heated to 70 ° C, a further 15 to 120 min. with the
Zahnscheibe gerührt und abgekühlt.Toothed washer stirred and cooled.
Bei der Herstellung der Suspensionen sind auch Temperaturen über 100°C möglich.Temperatures above 100 ° C are also possible when producing the suspensions.
Aus energetischen und anlagentechnischen Gründen sind jedoch nur Temperaturen bisFor energetic and technical reasons, however, only temperatures are up to
100°C sinnvoll.100 ° C makes sense.
Das Endprodukt hat einen Aluminiumsulfatgehalt, ausgedrückt als Al O3, von überThe end product has an aluminum sulfate content, expressed as Al O 3 , of over
8 bis 15 Gew.-%, bevorzugt von 10 bis 12 Gew.-%, und einen Gehalt an Bentonit von 1 bis 7 Gew.-%, bevorzugt von 2 bis 6 Gew.-%.( Alle angegebenen Konzentrationen in8 to 15% by weight, preferably 10 to 12% by weight, and a bentonite content of 1 to 7% by weight, preferably 2 to 6% by weight
Prozent sind als Gewichtsprozente zu verstehen.)Percentages are to be understood as percentages by weight.)
Die erfindungsgemäßen Suspensionen eignen sich in hervorragender Weise zumThe suspensions according to the invention are outstandingly suitable for
Beschleunigen des Abbindens und Erhärtens von Zement und diesen enthaltendeAccelerate the setting and hardening of cement and containing it
Gemischen. Besondere Einsatzbereiche sind der Spritzmörtel und Spritzbeton sowohl beim Trocken- als auch Nassspritzverfahren. Die Suspensionen werden dabei bevorzugt im Bereich von 1 bis 15%, bezogen auf das Bindemittel, eingesetzt.Mixtures. Special areas of application are sprayed mortar and shotcrete in both dry and wet spraying processes. The suspensions are preferably used in the range from 1 to 15%, based on the binder.
Die folgenden Beispiele beschreiben den Erfϊndungsgegenstand näher ohne diesen zu beschränken. HerstellungThe following examples describe the subject matter in more detail without restricting it. manufacturing
Beispiel 1 :Example 1 :
In einen 1,2 1 Doppelmantelreaktor mit Rührer wurden 535,5 g Wasser vorgelegt und 60g Bentonit eingerührt. Zu dieser Mischung wurden unter Rühren 904,5 g festes Aluminiumsulfat mit einem Al2O3-Gehalt von 11% und einem Sulfatgehalt von 47% zugegeben. Es wurde auf 58°C aufgeheizt, 60 Min. bei dieser Temperatur gerührt und danach abgekühlt. Die entstandene Suspension hatte eine Brookfϊeld Viskosität (DV-II, 20°C, 60 Upm) von 900 mPas, CSB: 160 ppm.535.5 g of water were placed in a 1.2 l double-jacket reactor with a stirrer, and 60 g of bentonite were stirred in. 904.5 g of solid aluminum sulfate with an Al 2 O 3 content of 11% and a sulfate content of 47% were added to this mixture with stirring. The mixture was heated to 58 ° C., stirred at this temperature for 60 minutes and then cooled. The resulting suspension had a Brookfield viscosity (DV-II, 20 ° C, 60 rpm) of 900 mPas, COD: 160 ppm.
Beispiel 2:Example 2:
In einen 200 1 Reaktor mit Zahnscheibe wurden 134,4 kg Aluminiumsulfatlösung mit einem Al2O3-Gehalt von 8% und einem Sulfatgehalt von 21,1% vorgelegt. Unter Rühren wurden 9 kg Bentonit zugegeben. Nach Erwärmen auf 33°C wurden 56,6 kg festes Aluminiumsulfat mit einem Al2O3-Gehalt von 17 % und einem Sulfatgehalt von 47% zugefügt. Der Reaktorinhalt wurde weitere 100 Min. bei 51 bis 59°C gerührt und danach abgekühlt. Die entstandene Suspension hatte einen pH- Wert von 2,4 und eine Brookfield Viskosität (DV-II, 20°C, 60 Upm) von 850 mPas, CSB: 170 ppm.134.4 kg of aluminum sulfate solution with an Al 2 O 3 content of 8% and a sulfate content of 21.1% were placed in a 200 l reactor with a toothed disk. 9 kg of bentonite were added with stirring. After heating to 33 ° C., 56.6 kg of solid aluminum sulfate with an Al 2 O 3 content of 17% and a sulfate content of 47% were added. The reactor contents were stirred for a further 100 minutes at 51 to 59 ° C. and then cooled. The resulting suspension had a pH of 2.4 and a Brookfield viscosity (DV-II, 20 ° C, 60 rpm) of 850 mPas, COD: 170 ppm.
Anwendungstechnische Beispiele:Application examples:
Vicat-Test:Vicat test:
Die Abbindezeiten wurden in Anlehnung an die Vicat-Methode, nach DIN EN- 196-3 ermittelt. Eingesetzt wurden 300 g Zement und 3 g Verflüssiger (1%). Der Wasser/Zement- Wert betrug 0,31. Der Zementleim wurde nach 10 min. Standzeit beschleunigt. Tabelle 1: Wirkung der erfindungsgemäßen Suspensionen auf die AbbindezeitenThe setting times were determined based on the Vicat method in accordance with DIN EN 196-3. 300 g of cement and 3 g of plasticizer (1%) were used. The water / cement value was 0.31. The cement paste was applied after 10 min. Tool life accelerated. Table 1: Effect of the suspensions according to the invention on the setting times
Als Vergleich diente eine handelsübliche Suspension (Meyco SA 160, MBT - Schweiz) mit einem Al2O3-Gehalt von 10,3 Gew.-% und einem CSB-Gehalt von 99 g/kg. Wie der Tabelle 1 zu entnehmen ist, haben im Vicat-Test die erfindungsgemäßen Suspensionen Vorteile gegenüber dem Vergleich.A commercially available suspension (Meyco SA 160, MBT - Switzerland) with an Al 2 O 3 content of 10.3% by weight and a COD content of 99 g / kg served as a comparison. As can be seen from Table 1, the suspensions according to the invention have advantages over the comparison in the Vicat test.
VergleichsbeispieleComparative Examples
Da in den Beispielen der EP 0 858 981 AI keine Mengenangaben gemacht werden, wurden die Mengen der entsprechenden Substanzen gemäß den Angaben in den Patentansprüchen und der Beschreibung gewählt.Since no amounts are given in the examples of EP 0 858 981 AI, the amounts of the corresponding substances have been chosen in accordance with the information in the claims and the description.
Nach Anspruch 4 der EP 0 858 981 AI muss der Gehalt an amorpher Kieselsäure mindestens 5 Gew.-% betragen. Gemäß der Aussage auf Seite 2, Zeile 55 kann der Abbindebeschleuniger bis zu 5 Gew.-% Bentonit enthalten.According to claim 4 of EP 0 858 981 AI, the content of amorphous silica must be at least 5% by weight. According to the statement on page 2, line 55, the setting accelerator can contain up to 5% by weight bentonite.
Weiterhin wurde auf organische Hilfsmittel verzichtet, um in den Abbindebeschleuniger keine CSB-haltigen Stoffe einzutragen. Es wurden also nach der Lehre dieses Patents CSB-freie bzw. nahezu CSB-freie Abbinde- und Erhärtungsbeschleuniger hergestellt, die zwingend drei Substanzen enthalten müssen. Folgende Ausgangsverbindungen wurden verwendet:Furthermore, organic aids have been dispensed with so that no COD-containing substances are added to the setting accelerator. According to the teaching of this patent, COD-free or almost COD-free setting and hardening accelerators were produced, which must contain three substances. The following starting compounds were used:
1. Handelsübliche, gesättigte Aluminiumsulfatlösung mit 8 Gew.-% Al2O3-Gehalt und 21,1 Gew.-% Sulfatgehalt1. Commercial, saturated aluminum sulfate solution with 8 wt .-% Al 2 O 3 content and 21.1 wt .-% sulfate content
2. Sipernat 570 (Degussa) als amorphe Kieselsäure2. Sipernat 570 (Degussa) as amorphous silica
3. Ca/Na-Bentonit3. Ca / Na bentonite
Vergleichsbeispiel 1:Comparative Example 1:
In 92,75 g Aluminiumsulfatlösung wurden nacheinander 5 g amorphe Kieselsäure und 2,25 g Bentonit eingerührt. Die entstandene Suspension wurde 1 Stunde gerührt.5 g of amorphous silica and 2.25 g of bentonite were successively stirred into 92.75 g of aluminum sulfate solution. The resulting suspension was stirred for 1 hour.
Vergleichsbeispiel 2:Comparative Example 2:
In 90,5 g Aluminiumsulfatlösung wurden nacheinander 5 g amorphe Kieselsäure und 4,5 g Bentonit eingerührt. Die entstandene Suspension wurde 1 Stunde gerührt.5 g of amorphous silica and 4.5 g of bentonite were successively stirred into 90.5 g of aluminum sulfate solution. The resulting suspension was stirred for 1 hour.
Vergleichsbeispiel 3:Comparative Example 3:
In 87,75 g Aluminiumsulfatlösung wurden nacheinander 10 g amorphe Kieselsäure und 2,25 g Bentonit eingerührt. Die entstandene Suspension wurde 1 Stunde gerührt.10 g of amorphous silica and 2.25 g of bentonite were successively stirred into 87.75 g of aluminum sulfate solution. The resulting suspension was stirred for 1 hour.
Tabelle 2: Wirkung der erfindungsgemäßen Suspensionen auf die AbbindezeitenTable 2: Effect of the suspensions according to the invention on the setting times
Wie der Tabelle 2 zu entnehmen ist, ist die erfϊndungsgemäße Suspension denen der Vergleichsbeispiele gemäß der EP 858 981 AI deutlich überlegen. As can be seen from Table 2, the suspension according to the invention is clearly superior to that of the comparative examples according to EP 858 981 A1.
Festigkeitenstrength
Die Festigkeiten wurden in Anlehnung an DIN 1164, Teil7 untersucht. Dabei wurden folgende Modifikationen vorgenommen:The strengths were examined based on DIN 1164, Part 7. The following modifications were made:
• Zuschlag: 0 bis 8 mm• Surcharge: 0 to 8 mm
• W/Z- Wert: 0,48 • Verflüssiger: 1%• W / Z value: 0.48 • Condenser: 1%
• Beschleunigerzugabe: 60 Min. nach Herstellung des Betons• Accelerator added: 60 minutes after the concrete was made
• Zement: 420 kg/m3 • Cement: 420 kg / m 3
• Beschleuniger: 8% bzgl. Zement• Accelerator: 8% for cement
Tabelle 3: Wirkung der erfindungsgemäßen Suspensionen auf die Früh- und EndfestigkeitenTable 3: Effect of the suspensions according to the invention on the early and final strengths
Als Vergleich diente eine handelsübliche Suspension (Meyco SA 160, MBT - Schweiz) mit einem Al2O3-Gehalt von 10,3 Gew.-% und einem CSB-Gehalt von 99 g/kg. Wie der Tabelle 3 zu entnehmen ist, ist die Wirkung der erfindungsgemäßen Suspensionen vergleichbar mit der CSB-belasteten handelsüblichen Suspension. A commercially available suspension (Meyco SA 160, MBT - Switzerland) with an Al 2 O 3 content of 10.3% by weight and a COD content of 99 g / kg served as a comparison. As can be seen from Table 3, the effect of the suspensions according to the invention is comparable to that of the commercially available suspension loaded with COD.

Claims

Patentansprüche claims
1. Suspensionen, dadurch gekennzeichnet, dass sie Aluminiumsulfat in Mengen von über 8 Gew.-% als Al O3 und dispergierten Bentonit in Mengen von 1 bis 7 Gew.-% enthalten.1. Suspensions, characterized in that they contain aluminum sulfate in amounts of more than 8% by weight as Al O 3 and dispersed bentonite in amounts of 1 to 7% by weight.
2. Suspensionen nach Anspruch 1, dadurch gekennzeichnet, dass sie Aluminiumsulfat in Mengen von 10 bis 12 Gew.-% Al2O3 als und dispergierten Bentonit in Mengen von 2 bis 6 Gew.-% enthalten.2. Suspensions according to claim 1, characterized in that they contain aluminum sulfate in amounts of 10 to 12% by weight of Al 2 O 3 and dispersed bentonite in amounts of 2 to 6% by weight.
3. Verfahren zur Herstellung von Suspensionen gemäß den Ansprüchen 1 und 2, dadurch gekennzeichnet, dass Aluminiumsulfat in Gegenwart von Bentonit in Wasser bei erhöhten Temperaturen, bevorzugt bei Temperaturen bis 100°C, verrührt wird, so dass eine homogene Suspension entsteht.3. Process for the preparation of suspensions according to claims 1 and 2, characterized in that aluminum sulfate is stirred in the presence of bentonite in water at elevated temperatures, preferably at temperatures up to 100 ° C, so that a homogeneous suspension is formed.
4. Verfahren zur Herstellung von Suspensionen gemäß den Ansprüchen 1 und 2, dadurch gekennzeichnet, dass in einem ersten Schritt Bentonit in einer Aluminiumsulfatlösung suspendiert wird und in einem zweiten Schritt festes Aluminiumsulfat in dieser Suspension bei erhöhter Temperatur, bevorzugt bis4. A process for the preparation of suspensions according to claims 1 and 2, characterized in that in a first step bentonite is suspended in an aluminum sulfate solution and in a second step solid aluminum sulfate in this suspension at elevated temperature, preferably to
100 °C, homogen suspendiert wird.100 ° C, is homogeneously suspended.
5. Verwendung der Suspensionen gemäß den Ansprüchen 1 bis 2 zur Beschleunigung des Abbindens und Erhärtens von Zement und diesen enthaltende Gemische. 5. Use of the suspensions according to claims 1 to 2 for accelerating the setting and hardening of cement and mixtures containing it.
EP03792403A 2002-08-23 2003-08-21 Suspensions Ceased EP1546060A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10238789 2002-08-23
DE10238789A DE10238789B4 (en) 2002-08-23 2002-08-23 Process for the preparation of suspensions and their use
PCT/EP2003/009256 WO2004018380A2 (en) 2002-08-23 2003-08-21 Suspensions containing aluminium sulphate

Publications (1)

Publication Number Publication Date
EP1546060A2 true EP1546060A2 (en) 2005-06-29

Family

ID=31197303

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03792403A Ceased EP1546060A2 (en) 2002-08-23 2003-08-21 Suspensions

Country Status (5)

Country Link
US (1) US7470317B2 (en)
EP (1) EP1546060A2 (en)
AU (1) AU2003264081A1 (en)
DE (1) DE10238789B4 (en)
WO (1) WO2004018380A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248780A1 (en) 2009-05-06 2010-11-10 BK Giulini GmbH Set- and hardening accelerator

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1724246A1 (en) * 2005-05-18 2006-11-22 I.C.R.S. Industrial Ceramic Reinforcement Solution S.r.L. Auxiliary substance for cement-based materials and the like
MX2010007596A (en) * 2008-01-11 2010-08-03 Constr Res & Tech Gmbh Aqueous accelerator mixture.
JP2014019623A (en) * 2012-07-20 2014-02-03 Denki Kagaku Kogyo Kk Suspension type cement quick-setting agent, and quick-setting cement concrete using the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0858981A1 (en) 1997-02-14 1998-08-19 Sika AG, vorm. Kaspar Winkler & Co. Hardening accelerator for cement
EP1167317A1 (en) 2000-06-21 2002-01-02 Sika AG, vorm. Kaspar Winkler & Co. Alkali-free set and hardening accelerator

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069062A (en) * 1973-05-08 1978-01-17 Sika Ag, Vormals Kaspar Winkler & Co. Additive for mortar and concrete
US4359339A (en) * 1980-12-16 1982-11-16 Nl Industries, Inc. Bentonite clay and water soluble aluminum salt compositions
SU956529A1 (en) * 1981-01-05 1982-09-07 Волжский Филиал Всесоюзного Научно-Исследовательского Института Абразивов И Шлифования Suspension for metal machining
JP2598646B2 (en) * 1987-08-13 1997-04-09 日本ピー・エム・シー株式会社 Dispersion method of bentonite powder
US4883536A (en) * 1988-08-05 1989-11-28 Aqualon Company Suspension of water-soluble polymers in aqueous media containing dissolved salts
CA2115390C (en) * 1993-03-22 1999-08-24 Bharat B. Patel Fluid composition comprising a metal aluminate or a viscosity promoter and a magnesium compound and process using the composition
DE4312290A1 (en) * 1993-04-15 1994-10-20 Degussa Precipitant and flocculant
DE4410728A1 (en) * 1994-03-28 1995-10-05 Sued Chemie Ag Auxiliary for mineral binder systems
AU723970B2 (en) * 1996-06-14 2000-09-07 Construction Research & Technology Gmbh Concrete spraying additives
EP0812812B1 (en) 1996-06-14 2003-01-29 Mbt Holding Ag Concrete spraying additives
JP3384547B2 (en) * 1998-11-30 2003-03-10 電気化学工業株式会社 Slag reduction agent
DE10029869C2 (en) * 2000-06-16 2003-10-30 Rex Ind Produkte Graf Von Rex Fiber-free, non-combustible, foamed insulation and fire protection material and process for its production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0858981A1 (en) 1997-02-14 1998-08-19 Sika AG, vorm. Kaspar Winkler & Co. Hardening accelerator for cement
EP1167317A1 (en) 2000-06-21 2002-01-02 Sika AG, vorm. Kaspar Winkler & Co. Alkali-free set and hardening accelerator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2004018380A3

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248780A1 (en) 2009-05-06 2010-11-10 BK Giulini GmbH Set- and hardening accelerator

Also Published As

Publication number Publication date
DE10238789A1 (en) 2004-03-04
AU2003264081A1 (en) 2004-03-11
US20060249055A1 (en) 2006-11-09
AU2003264081A8 (en) 2004-03-11
DE10238789B4 (en) 2006-01-05
US7470317B2 (en) 2008-12-30
WO2004018380A3 (en) 2004-05-21
WO2004018380A2 (en) 2004-03-04

Similar Documents

Publication Publication Date Title
DE2007603C3 (en) Additive for hydraulic cement mixes and process for the preparation of an easily dispersible hydraulic cement mix
EP0260538B1 (en) Use of expandable synthetic lamellar silicates in aqueous drilling or borehole treatment fluids
EP0711260B1 (en) Use of basic aluminium sulphates as alkali-poor cement accelerating admixtures
WO2008006410A1 (en) Stable air-placed concrete accelerator dispersion with a high active substance content
WO1998018740A1 (en) Solidifying and hardening accelerator for hydraulic binders
DE69120431T2 (en) METHOD FOR PRODUCING BENTONITE SLURRIES WITH HIGH SOLIDS
CH633500A5 (en) METHOD FOR PRODUCING CONCRETE WITH HIGH RESISTANCE TO CORROSION AND CEMENT AND ADDITIVES.
WO2009086998A1 (en) Aqueous accelerator mixture
WO2006097316A1 (en) Hardening and setting accelerator additive, use of the latter and method for producing said additive
DE69003798T2 (en) Fungicidal and anti-corrosive paint pigments.
EP0584502B1 (en) Process for the spontaneous precipitation of sulfates dissolved in water as calcium aluminium sulfate and the application of this process for the preparation of low-chloride gypsum-anhydrite containing aluminium oxide
EP3142989A1 (en) Stabilized solidification and setting accelerator for hydraulic binders
CH646929A5 (en) METHOD FOR PRODUCING LIGHTWEIGHT MATERIAL AND LIGHTWEIGHT MATERIAL PRODUCED BY THE PROCESS.
DE1134783B (en) Process for the production of barium metaborate pigments coated with silicon dioxide
EP0798300B1 (en) Aluminium compounds
DE10238789B4 (en) Process for the preparation of suspensions and their use
EP0467165B1 (en) Solids suspensions stable against sedimentation and process for their preparation
AT403276B (en) CEMENT ACCELERATOR
EP0287589B1 (en) Thickener for thixotropic coating masses
DE2745023A1 (en) MORTAR MATERIALS FROM IRON II SULPHATE AND THE PROCESS FOR THEIR PRODUCTION
DE102019105573A1 (en) Process for the preparation of a granular animal litter
DE3205876C2 (en) Process for the production of storable sealing or insulating compounds based on bitumen emulsions suitable for one-component application
DE2449802A1 (en) PROCESS FOR THE MANUFACTURING OF MINERAL FILLERS, FILLERS MANUFACTURED BY THE PROCESS AND THEIR USE
EP2498595B1 (en) Method for producing animal litter
DE2738415B2 (en) Calcium sulphate fibers with inorganic coatings

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050323

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 04B 22/02 A

TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: KURITA WATER INDUSTRIES LTD.

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20161015